Lubricating composition



' Patented Sept. 23, 1952 UNITED "sTAr-Es PATE T,.orrica signor, to Aluminum Company of America, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Application December 17, 1949; Serial No. 133,684 In Canada June 10, 1947- r This .invention relates to improved lubricants, such as oils, greases or semi-fluid oils, containing asa major lubricating componenthydrocarbon oil .of natural or synthetic .origin. In particular, the invention relates to, lubricating compositions of..this .type having improved extreme pressure characteristics.

Requirements upon lubricants, by developments in. mechanical .design. are rigid. and drastic. In many instances pressures at bearingsuriaces are higher than those which petroleum oils will normally withstand.."Illustrative are the conditions encountered "in the lubrication .of automotive hypoid gears, heavily. loaded .mill pinion gears, naval. turret gears, 'and the like.. In many machinesoperation is, at least in part, under conditions of thinfilm lubrication or under similar conditions where film strength, .oiliness and anti-wear characteristics of high order are required of the lubricating medium.

The principal object of this invention isthe provision of a new composition of matter consisting of a compounded lubricating product possessing extreme pressure characteristics of a high order. Further objects include the provision of a compounded lubricant containing as. a major hydrocarbon lubricating component which may be oil "or grease of natural or synthetic origin, the lubricant having a superior combination of high film strength, oiliness and anti-wear characteristics.

In accordance with this invention these objects are achieved in substantial part by providing a lubricant, the essential lubricating components of which are a major amount of a hydrocarbon lubricatingcomponent which may be oil or grease andaminor amount of a bodyof boron fluoride and a substance selected from the class consisting of unmodified alcohols containing at least 3 carbon .atoms, alcohol-ethers and ethers more specifically described below. The proportion of this body to thehydrocarbon component should besuch, however, that the mixture contains at least 0.001 per cent by weight of boron fluoride (BFs) while, on the other hand, more than 3 per cent does not improve the lubricant. Within this range it has been-found that the best results are obtained by providing from 0.1 to 1.0 per cent of boron fluoride in the final lubricant mixture. The choice of the particular body to be employed and its boronfluoride-content will of course depend on such matters as cost,.ease of mixing and the nature of the lubrication problem.

The principal advantages-and effectiveness of this new compounded lubricant are maintained 3 Claims (01. 252 49.s

when, in addition to-the abovementioned essential components there are likewise-present in the lubricatingv composition other components added to improve some specific characteristic or property thereof, such as, viscosity, pour point, oilisness, .flow anti-wear characteristics film strength or the like, the efiect of the defined boronjfiuoride-containing body, when similar, beinglargely additive. Such diluents, '0r;,additions may. therefore, vfor the purposes .of, this "invention be regarded as a non-essential portion .of the composition, regardless of; their, specific- .beneficial .or functional eliec t. Thesamejm iy besaid of substances known .as extreme pressure additives, such as substances composed qt chlorine, sulphur or. lead containing compoundsaor materials, it being observable'th at'the presence of the defined boron fluoride-containing bodies is efiective to increase the extreme pressure characteristics of the compositions even when other extreme pressure. additives are; present;v

The organic BFa body, which in accordance with this invention isblended with the hydrocarbon component, maybe, prepared in various ways but is, for the most part, conveniently prepared by exposing the unmodified alcohol, alcohol-ether or ether to direct contact with gaseous BF3. This can be easily accomplished under ordinary atmospheric pressure by bubbling the gaseous BF: through the alcohol, alcohol-ether or ether in a liquid state. If the organic material is not liquid at room temperature it-should be heated to and maintained at atemperature slightly above its melting point, say 5; or 1 0 C. Although the rate of flow of the'gas isnot critical with respect to formation of the'BFa additive yet the fiow should be controlledto avoidundue loss. The rate, of acceptance of,:the BF: .bythe alcohol, alcohol-ether or ether is improved if the liquid is stirred asthe gas. is, introducedjThe amount of. BF3 accepted, by the-alcohol, alcoholether or ether is indicatedflby. the;increasejin weight oi -the treated mass. The introduction of the gas-may therefore be continued, until. a predetermined increase in weight,- shortotsatviration, has been obtained or the flow .of gasmay be prolonged until no further increase in weight is observed at which point the alcohol, alcohol: ether or ether is considered to be saturated. with. BFs. Generally, it is most convenient to follow the latter procedure. "Inbo-th cas'es; ,however,'.the length of time required toj'reach 1the flend,point can be easily determined forjthe' materialbeing treated and thus make itj'possible to. introduce the-desired amount of BFawithout having to test a charge at intervals during the period of treatmerit. lllthough each alcohol, alcohol-ether or ether a h ve i nt s t at o t or the desired 3F; content for various ma e a s thi oes ot t a t r m t e val e of the Bi s-containing body in improving the load bearing quality of a hydrocarbon lubricant.

Qth r me ho of n od ing BFs can b em o o cou e Fo amp e. he a l.

alcohol-ether or ether may be exposed to the gas at higher temperatures and pressures and. thus shorten the time required to introduce the desired may become thicker as the introduction of BFs amount of BF's. Naturally, the temperature and pressure should be such that the alcohol, alcohol the organic material with BFalS to add com pounds to it whichcan be decomposed with the release of BFs. Such compounds as NHBF, BFs'NHa, the heavy metal fluoborates or even other organic materials previously treatedwith BFs may be employed. To effiect decomposition it is usually necessary to heat the mixtureof alcohol, alcohol-ether or other and the BFa-com taming substance. Further, it may be desirable to remove any residues resulting from the decomposition.

he amou t o BFa that can be introduced into different alcohols, alcohol-ethers or ethers'will vary, as mentioned above, however, from to p r entby w ht is preferred where. the saturation point permits it. In any case, the alcohols, alcoholaethers or others should. be treated with sufiicient fluoride to provide the desired BFc' content in the lubricating composition as only a. minor proportion of the additive is employed.

resultant product may. in some instances, be an actual compound, there being some, evidence to indicate that such is its nature, or it may be an additive or coordinate compoundv or even a ol t on or is e i pref r. however, to erm e p o uct a body or composition OQnSisting essentially of a substance selected from the cla s qm st ns of unm e a coho containing atleast 3 carbon atoms, alcohol-ethers and ethers an 2 an therefore, not to characterize the state of association of the fluoride and the organic substance. i any event. the un odified lcohols. containing at least 3 carbon atoms, alcohol-others a d. fi l t a c tors 0f BFa to produce a body or substance having positive advantages as.

a dit ve. in ubr cating compositions,

The following list of alcohols, alcohol-ethers and others is illustrative of the class which when. treated with BE; produce the bodies just olescribed straight chain normal alkyl monohydric alcohols such as propyl through octadecanol as w l a higher p e ular wei ht alcohols of the type 1 represented by tetracosanel and tria acontanol; alkyl, aromatic, and cyclic (and polyhydroxy derivatives thereot) ethers of monoand polyhydric alkyl, aromatic and cyclic alcohols such as ethylene glycolmonomethyl ether, ethylene glycol diethyl ether, ethylene glycol mono octadecyl ether, ethylene glycol ethylbutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, propylene lycol methyl ether, propylene glycol 4-biphenyl ether, tripropylene glycol n-butyl ether, polypropylene glycol methyl ether (mol. wt. 496 to 3000), dodecyl 2,3-dihydroxypropyl ether, 1,3- dihydroxypropyl-2 hexadecyl ether, phenyl decyl ether, p-tolyl dodecyl ether, naphthyl undecyl 7 ether, hydroxycyclohexyl octadecyl ether and proceeds and the melting point of the end product may be. higher than that of the original alcohol, alcohol-ether or ether. ether or ether is not decomposed to any sub 1. stantial degree. Another method of contacting Such changes do not affeet the advantages gained from the presence of the BFs-contairfing bodies in a hydrocarbon lubricant, certainly the results of the invention do not depend upon or are responsive to any peculiar chemical or physical qualities of the BFa-containing additive, rather they depend upon the admixture of the additive with the hydrocarbon lubricant.

The action of these organic BFB bodies in a hydrocarbon lubricant is positive and specific to increase the load bearing capacity of the lubricant and, in many instances, to definitely improve its anti-wear characteristics. The amount of these organic BF: bodies necessarily present to produce these specific effects is very small. The amounts used, should in any case, as mentioned above, provide at least 0.001 per cent byweight of BF: in the final mixture. The amount of any given BFa-containing body desirably. presentto produce optimum effects in any particular hydrocarbon lubricant can be readily determined by simple trial, the optimum usually being found within the range of 0.5 to 5 per cent by weight of the alcohol, alcohol-ether or ether BF: body. Amounts below about 0.01 per cent by weight often do not produce sufiicient effect to he usually characterized as commercial, but the efiect produced issuch as to be useful under exceptional conditions. One may use a .relatively small amount of an additive containing a substantial quantity of BF: or a larger amount of thesame or another additive which contains a smaller proportion of BFs to introduce a given quantity of BF: into the hydrocarbon component. In any event, the organic 'BFs additive forms a minor amount or proportion of the lubricating composition.

The, load bearing qualities of a lubricant may be, relatively determined by various methods. The. method used to obtain the comparative data hereinafter set forth is practiced on a Falex ma.- chine and consists in submitting small quantities of the lubricant tothe action of a rotating steel journal rotated in contact with two V-shaped bearing blocks. During testing measurable. pressure was applied to the rotating journal by use of an automatic loading device. The two bearing blocks and the journal were submerged in the lubricant sample throughout the tests. In each test load was applied and allowed to reach 500' pounds; at'this load the journal was then run for 5 minutes; thereafter the load was gradually increased until lubrication failure occurred. The: load at the time of failure is designated as the failure load. In general, the failure loads are reproducible within pounds at lower pressure and 300 pounds at higher pressure; the results are not absolute but are comparative with a standard. run under the same conditions. In the tests by which the results set forthin the following table: were secured, the hydrocarbon oil was in all cases in the .011.

the same, being a-straight mineral oil. In all casesl per cent by weight of additive was present The additive had, been prepared by "passing- BF; through the alcohol, 3.100110128131181 or ether until. the weight of the, body became, substantially constant, that is, the organic material became saturated with the 's, as has been described hereinabovew Each comparative test was run on two samples, one sample being the oil containing 1 per cent by weight of an alcohol,

alcohol-ether or ether, the other sample being the oil containing the same weight of a BFa-containing body. In the first column of the table the nature of the additive is set forth, in the second column is listed the BF:; content of the treated material, in the third column is the BF: content of the lubricant, in the fourth column the failure load in pounds is given and in the fifth column is shown the percentage increase in failure load caused by the presence of the El 's-containing body.

6 consisting essentially of asubstahce selected from the class consistingof unmodified alcohols containing at least three carbon, atoms, alcoholethers and ethers and BFa, said. body being pre pared by exposing said substances to direct contact with a substance selected from the class consisting of gaseous BF3 and'decomposable'fcom pounds yielding gaseousBFe and being present 'in such amount that the lubricating composition contains from 0.001 to 3 per cent by weight of Percent Percent Failure Percent- Additive BFa in BF: in Lead m age Additive Lubricant Pounds Increase Octyl alcohol 1 Octyl alcohol BFa. 700 Tetradecanol 348 Tetradecanol B11. Cetyl alcohol 204 Cetyl alcohol BFa 0 Polyethylene glycol (mol. wt. 200). 88 87 Polyethylene glycol BF Phenyl cellosolve 750 180 Phenyl cellosolve B Methyl cellosolve 75 160 Methyl cellosolve BFs 64. 64 l, 950 Diethyl cellosolve 750 90 Diethyl cellosolve BF 54. 5 .55 1, 450 Diethyl carbitol 800 163 Diethyl earbitol BF 50. 5 2, 110 N-Hexyl ether 800 193 N-Hexyl ether BFa 28. 3 28 2, 350

1 Greater than.

glycol monoethyl ether.

The machine on which the tests were run had a capacity of 4500 pounds. Where this capacity was approximated or exceeded the failure load is indicated above as being greater than 4000 pounds. These tabulated results are indicative of the improvement obtained by the practice of this invention. In general, torque and temperature values obtained during these tests indicated that the organic B-F3 body improved friction qualities and observations simultaneously made indicated increases in anti-wear characteristics.

In compounding lubricant compositions of the type herein described and claimed the organic BF3 additive may merely be mixed with the hydrocarbon lubricants, the properties of which are to be improved. Where the additive is insoluble in the lubricant or it is desired to incorporate therein amounts in excess of solubility, emulsions or dispersions may be prepared according to known principles.

This application is a continuation-in-part of my prior application Serial No. 714,910 filed December 7, 1946, and entitled Lubrication Composition, now abandoned.

Having thus described my invention and the known advantages thereof, I claim:

1. A lubricating composition comprising a major proportion of a hydrocarbon lubricating oil blended with a minor proportion of a body hol to direct contact with a substance selected from the class consisting of gaseous BF3 and decomposable compounds yielding gaseous BF: and being present in such amount that the lubricating composition contains from 0.001 to 3 per cent by weight of BFs, said lubricating composition possessing extreme pressure characteristics superior to those exhibited by a similar composition in which the minor proportion aforesaid consists of cetyl alcohol.

3. A lubricating composition comprising a major proportion of a hydrocarbon lubricating oil blended with a minor proportion of a body consisting essentially of octyl alcohol and BFs, said body being prepared by exposing octyl alcohol to direct contact with a substance selected from the class consisting of gaseous BF3 and decomposable compounds yielding gaseous BFs and being present in such amount that the lubricating composition contains from 0.001 to 3 per cent by weight of BF3, said lubricating composition possessing extreme pressure characteristics superior to those exhibited by a similar composition in which the minor proportion aforesaid consists of octyl alcohol.

EGBERT MASON KIPP.

(References on following page) 7 REFERENCES CITED [The foilowing references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2 ,053;4'74 Graves Sept. 8, 1936 2,160,917 Shoemaker June 6, 1939 2,266,060 Miller Dec. 16, .1941

OTHER REFERENCES Boron .Trifiuorid and its Derivatives Booth 'et alufiohn Wiley and Sons-1949, pp. 61-64 and 68-71. 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A HYDROCARBON LUBRICATING OIL BLENDED WITH A MINOR PROPORTION OF A BODY CONSISTING ESSENTIALLY OF A SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF UNMODIFIED ALCOHOLS CONTAINING AT LEAST THREE CARBON ATOMS, ALCOHOLETHERS AND ETHERS AND BF3, SAID BODY BEING PREPARED BY EXPOSING SAID SUBSTANCES TO DIRECT CONTACT WITH A SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF GASEOUS BF3 AND DECOMPOSABLE COMPOUNDS YIELDING GASEOUS BF3 AND BEING PRESENT IN SUCH AMOUNT THAT THE LUBRICATING CMPOSITION CONTAINS FROM 0.001 TO 3 PER CENT BY WEIGHT OF BF3, SAID LUBRICATING COMPOSITION POSSESSING EXTREME PRESSURE CHARACTERISTICS SUPERIOR TO THOSE EXHIBITED BY A SIMILAR COMPOSITION IN WHICH THE MINOR PROPORTION AFORESAID CONSISTS OF SAID SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF UNMODIFIED ALCOHOLS, ALCOHOL-ETHER AND ETHERS. 